Adsorbents and methods of use

ABSTRACT

Systems, methods and compositions for reducing the heteroatom content of hydrocarbon feed using transition metal complexes and adsorption techniques. The transition metal complexes include titanyl, hafnyl and zirconyl complexes activated using one or more hydroperoxides or peracids. The activated adsorbents are incorporated into one or more vessels as an adsorption bed for adsorbing the heteroatoms present in hydrocarbon feeds. The systems, methods and compositions separate the heteroatoms passed through the system by contacting the adsorption compositions with the heteroatoms of the hydrocarbon feed, adsorbing the heteroatom to the adsorption material, further allowing for the retrieval of a hydrocarbon product having a reduced heteroatom content.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the priority and benefit of U.S. PatentApplication No. 62/138,475 filed Mar. 26, 2015, entitled “ADSORBENTS ANDMETHODS OF USE”, the content of which is incorporated herein byreference.

FIELD OF THE TECHNOLOGY

The following relates generally to embodiments of adsorbents and methodsof using adsorbents. More specifically, the following relates toadsorbents with an affinity for binding heteroatom compounds present inhydrocarbon feed streams.

BACKGROUND

Hydrocarbon fluids including crude oils and heavy crude oils containheteroatoms that should be removed and refined prior to the hydrocarbonbeing transported or used for commercial consumption. These heteroatomsinclude compounds containing such elements as sulfur, nitrogen, nickel,vanadium and acidic oxygenates. The heteroatoms may be present incompounds at quantities that negatively impact the refinery processingof the crude oil fractions.

Crude oils that have unsuitable heteroatom properties limit the crudefrom being economically transported or processed using conventionalfacilities. These types of crude hydrocarbons may be commonly referredto as “disadvantaged crudes.” Disadvantaged crudes often containrelatively high levels of residue. High residue crudes may be treated athigh temperatures to convert the crude to coke. Alternatively, highresidue crudes are typically treated with water at high temperaturesthrough the use of steam cracking to produce less viscous crudes and/orcrude mixtures. During processing, water removal from the less viscouscrudes and/or crude mixtures may be difficult using conventional means.

Disadvantaged crudes may include hydrogen deficient hydrocarbons. Whenprocessing hydrogen deficient hydrocarbons using previously knownmethods, consistent quantities of hydrogen are generally needed to beadded, particularly if unsaturated fragments resulting from crackingprocesses are produced. Hydrogenation during processing, which typicallyinvolves the use of an active hydrogenation catalyst, may be needed toinhibit unsaturated fragments from forming coke. Hydrogen is costly toproduce and/or costly to transport to treatment facilities.

Disadvantaged crudes often include organically bound heteroatoms (forexample, sulfur, oxygen, and nitrogen). Organically bound heteroatomsmay, in some situations, have an adverse effect on catalysts. Alkalimetal salts and/or alkaline-earth metal salts have been used inprocesses for desulfurization of residue. These processes tend to resultin poor desulfurization efficiency, production of oil insoluble sludge,poor demetallization efficiency, formation of substantially inseparablesalt-oil mixtures, utilization of large quantities of hydrogen gas,and/or relatively high hydrogen pressures.

Some processes for improving the quality of crude include adding adiluent to disadvantaged crudes to lower the weight percent ofcomponents contributing to the disadvantaged properties. Adding diluent,however, generally increases costs of treating disadvantaged crudes dueto the costs of diluent and/or increased costs to handle thedisadvantaged crudes. Addition of diluent to disadvantaged crude may, insome situations, decrease stability of such crude.

In the United States and other countries around the world, there hasbeen emphasis by governments to pass stricter standards for hydrocarbonfluid being used commercially that derive from crude oils. For example,in the US, it is strictly required that hydrocarbon fluids, such ason-road diesel fuel, meet the required ultra-low sulfur specificationsof 15 ppm sulfur. Due to the extremely low nature of the governmentimposed specifications, the oil and fuel industry has been continuouslyevolving their heteroatom removal processes to realize greater andgreater heteroatom removal without incurring exorbitant expenses.

One method of removing unwanted heteroatoms from hydrocarbon fluids isthrough the use of adsorbents or adsorbent beds which attract, bind,separate and remove the heteroatom containing hydrocarbon compoundspresent in hydrocarbon feeds coming in contact with the adsorbent. Theeffectiveness of an adsorbent may depend on the adsorbent's bindingaffinity and ability to attract the heteroatoms in the hydrocarbonfluid. In order to be economical, the heteroatom compound attracted toan adsorbent should be removed from the adsorbent in a manner thatallows the adsorbent to be used again. Many adsorbents strongly bindsulfur and other heteroatom compounds, but require high temperatures andsevere conditions to both adsorb and to remove the heteroatom compounds,often burning them in the process. Additionally, many refinery productsor intermediates cannot be heated to severe temperatures withoutinducing undesired chemical changes to the hydrocarbon feeds. Thus,there is a need for a new and novel adsorbent capable of bindingheteroatoms such as sulfur and nitrogen compounds with a high affinity,yet also capable of easily releasing those heteroatoms at lowtemperatures and mild conditions.

Advantages of the system and methods described herein over the priorart, include the ability of the adsorbents to be selectively modifiedand fine-tuned with various alcohol and polyol functional groupsattached to the metal complex of the adsorbent, allowing for theadsorbent to have an increased affinity and adsorbing strength forparticular characteristics of the heteroatoms being removed from thehydrocarbon feeds as well as selectivity for one or more classes ofheteroatoms. The adsorbents of the disclosed system and methods alsoenjoy an advantage of heteroatom removal from the heteroatom-boundadsorbent at low temperatures and pressures by contacting theheteroatom-bound adsorbent with one or more solvents such as ahydroperoxide or peracid to regenerate the adsorbent at low temperaturesand pressures.

SUMMARY OF THE TECHNOLOGY

A first embodiment of this disclosure relates generally to an adsorbentcomposition comprising a metal complex including a titanyl, wherein atitanium molecule of the titanyl is covalently bound to an alcohol or apolyol; and an inorganic oxide support of the metal complex bound to thetitanium molecule of the titanyl.

A method for reducing a heteroatom content of a hydrocarbon feedcomprising the steps of providing an adsorbent having a metal complexbound to an inorganic oxide support, wherein the metal complex is atitanyl having a titanium molecule covalently bonded to an alcohol orpolyol; contacting the adsorbent with a hydroperoxide or a peracid,forming an activated adsorbent; contacting the activated adsorbent withthe hydrocarbon feed; binding a heteroatom present in the hydrocarbonfeed to the activated adsorbent, forming a heteroatom-bound adsorbent,leaving behind a hydrocarbon feed having a reduced heteroatom content;and separating the hydrocarbon feed having the reduced heteroatomcontent from the heteroatom-bound adsorbent.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts a partially exposed view of an embodiment of a system forreducing the heteroatom content of a hydrocarbon feed.

FIG. 2 depicts a partially exposed view of an alternative embodiment ofa system for reducing the heteroatom content of a hydrocarbon feed.

FIG. 3 depicts a flow chart describing an embodiment of a method forreducing the heteroatom content of a hydrocarbon feed.

FIG. 4 depicts a flow chart describing an alternate embodiment of amethod for reducing the heteroatom content of a hydrocarbon feed.

FIG. 5 depicts another alternative embodiment of a method for reducingthe heteroatom content of a hydrocarbon feed.

FIG. 6 depicts a flow chart of an alternative embodiment of a method forreducing the heteroatom content of a hydrocarbon feed using a pluralityof adsorbent beds in an adsorbent bed system.

DETAILED DESCRIPTION

Although certain embodiments are shown and described in detail, itshould be understood that various changes and modifications may be madewithout departing from the scope of the appended claims. The scope ofthe present disclosure will in no way be limited to the number ofconstituting components, the materials thereof, the shapes thereof, therelative arrangement thereof, etc., and are disclosed simply as anexample of embodiments of the present disclosure.

As a preface to the detailed description, it should be noted that, asused in this specification and the appended claims, the singular forms“a”, “an” and “the” include plural referents, unless the context clearlydictates otherwise.

Certain embodiments discussed in detail throughout this application maycontain terms herein which may be defined as follows:

An “adsorbent” may refer to a solid substance that has a propertyenabling the attachment one or more other substances (known as the“adsorbate”) to the surface of the adsorbent either throughchemisorption, which involves covalent bonding, or physisorption,involving intermolecular forces between the adsorbent and the adsorbate,which may include Van der Waals forces, electrostatic forces or hydrogenbonding in some embodiments. The adsorbent may be a porous material, andthe adsorption process may occur at the wall of the adsorbent's pores orat a particular site inside the pore of the adsorbent.

An “adsorbent bed” may refer to a vessel, tube, pipe or other containerfilled with adsorbent. The adsorbent bed may be incorporated as part ofa chemical reactor, distillation column or other equipment known or usedin the art.

An “alcohol” may refer to an organic compound characterized as havingone or more hydroxyl groups attached to a carbon atom of an alkyl group(hydrocarbon chain). The alkyl group may be represented by thedesignation of an “R” group. The most basic formula for an alcohol maybe depicted as R—OH.

A “functional group”, may refer to a portion of a molecule that has arecognizable or classified group of bound atoms. The functional groupmay give a substance its molecular properties. Throughout thisapplication a functional group may be designated with as an R group invarious chemical formulas and structures. As understood by individualsskilled in the art, a R group designated in a chemical formula may be anelement of the Periodic Table of Elements or a functional group, unlessotherwise specifically denoted as a particular element or functionalgroup. Examples of functional groups may include alkanes, alkenes,alkynes, aromatics, heterocyclics, alcohols, haloalkane, aldehyde,ketone, ether, ester, carboxylic acid, amine, amide, nitrile, nitrite,nitrate, chromate, carbonate, bicarbonate, imine, sulfhydryl, carbonyl,carboxyl, amino, phosphate, hydrogen phosphate, dihydrogen phosphate,sulfate, sulfite, thiosulfate, oxides, oxalate, formate, cyanide,acetate, permanganate, ammonium, etc.

A “heteroatom” may refer to any atom of a hydrocarbon that is neitherhydrogen nor carbon. Heteroatom containing compounds found in ahydrocarbon feed may include in a mixture of one or moreheteroatom-containing hydrocarbon compounds comprising sulfur, nitrogen,oxygen, phosphorous, chlorine, bromine, iodine, nickel, vanadium or ironheteroatoms. Common sulfur containing contaminants mixed withhydrocarbons in a hydrocarbon feed may include, but are not limited to,mercaptans, sulfides, disulfides, thiophenes, benzothiophenes,dibenzothiophenes and benzo-naphthothiophenes. Other heteroatoms, mayinclude heterocyclic heteroatom compounds such as aziridine, azirine,thiirane, thiirene, diazirine, oxaziridine, azetidine, azete, thietane,thiete, diazetidine, dithietane, dithiete, pyrrolidiine, pyrrole,thiolane, thiophene, imidazolidine, imidazole, pyrazole, pyrazolidine,oxazolidine, oxazole, isooxazolidine, isoxazole, thizolidine, thiazole,isothiazolidine, isothiazole, dithiolane, triazoles, furan, oxadiazole,thiadiazole, dithiazole, tetrazole, piperdine, pyridine, thiane,thiopyran, piperazine, diazones, morpholine, oxazine, dithiane,dithiine, triazone, trithiane, tetrazine, azepane, azepine, thiepane,thiepine, homopiperazine, diazepine, thiazepine, azocane, azocine, andcombinations thereof.

A “heteroatom content” may refer to the weight of the heteroatomcomponent in the hydrocarbon feed. For example, in a hydrocarbon feed,the heteroatom content may be expressed as a weight fraction or weight %(wt %) of the heteroatom over the total weight of thehydrocarbon/heteroatom mixed together (hereinafter “hydrocarbon feedmixture”):

${\frac{{weight}\mspace{14mu} {of}\mspace{14mu} {the}\mspace{14mu} {heteroatom}\mspace{14mu} {component}}{{{tot}{al}}\mspace{14mu} {weight}\mspace{14mu} {of}\mspace{14mu} {the}\mspace{14mu} {hydrocarbon}\mspace{14mu} {feed}\mspace{14mu} {mixture}} \times 100} = {{wt}\mspace{14mu} {\%.}}$

A “heteroatom-bound adsorbent” may refer to one or more heteroatommolecules adsorbed to the surface of an adsorbent.

A “hydrocarbon” may refer to a substance that has primary components ofhydrogen and carbon. Examples of hydrocarbons may include, but are notlimited to both saturated and unsaturated hydrocarbons, aromatichydrocarbons, alkanes, alkenes, alkynes, aryls and cycloalkanes.

A “hydrocarbon feed” may refer to a stream of hydrocarbons. Thehydrocarbon feed may include, but is not limited to, crude oils, heavyor extra heavy crude oils, crude oils containing significant quantitiesof residue or pitch, bitumen, disadvantaged crudes, contaminatedhydrocarbon streams, hydrocarbons derived from tar sands, shale oil,crude atmospheric residues, asphalts, hydrocarbons derived fromliquefying coal and hydrocarbons obtained from a refinery process ormixtures thereof. A hydrocarbon feed may include hydrocarbons,hydrocarbon distillates and/or fractions and may include a mixture ofone or more heteroatoms.

A “hydroperoxide” may include any chemical compound having the generalformula ROOH, wherein R is an element of the Periodic Table of Elementsor a functional group.

An “inorganic oxide” may refer to a binary compound of oxygen bound toan inorganic element of the Periodic Table of Elements or an inorganicfunctional group.

A “metal complex” may refer to substance or compound having a centralatom or ion, such as a metal atom, transition metal atom or an ionacting as a coordination center surrounded by an array of boundmolecules, ligands or complexing agents. A metal complex may also bereferred to as a “coordination complex”.

A “peracid” (also known as a peroxy acid) may refer to a compound havinga peroxy group (—O—O—) and an acidic group. The peracid may have thegeneral formula

wherein R is an element of the Periodic Table of Elements, an inorganicor an organic functional group thereof.

A “polyol” may refer to an alcohol having more than one hydroxylfunctional (—OH) group. For example, diol, triol, sugars, inositols,etc. A polyol may sometimes be referred to as a polyhydric alcohol,polyhydroxy alcohol or polyalcohol.

A “reduced heteroatom content” may refer to a substance or compound(such as a hydrocarbon feed) having an amount of heteroatoms presentthat is less than the amount of heteroatoms of a starting material. Forexample, a hydrocarbon feed with a reduced heteroatom content may referto a hydrocarbon feed that has less heteroatoms present than theinitial, starting hydrocarbon feed prior to the removal of anyheteroatoms.

A “regenerated adsorbent” may refer to an adsorbent that has previouslyadsorbed an adsorbate, and subsequently has had the adsorbate removed,allowing for the adsorbent to further adsorb another adsorbate.

A “solvent” may refer to a component of a solution capable of dissolvingand/or diluting another substance (referred to as the “solute”). In someinstances a solvent may dissolve the solute entirely, while in otherinstances, the solvent may not dissolve all components of the solute.For example, in heavy oil processes, the solvent may not dissolve thesolute entirely. Components, such as the asphaltene, of the heavy oilmay not dissolve or may only partially dissolve with certain solvents.

A “support” may refer to a material with a high degree of surface areawhich an adsorbent may be affixed or bonded to. An adsorbent may bedispersed over the support surface to maximize the surface area of theadsorbent being used. Embodiments of the support may be inert, howeverin alternative embodiments the support may also participate orfacilitate a chemical reaction.

A “titanyl” may refer to chemical group comprising titanium and oxygenmolecules covalently bonded, forming a TiO⁻² cation. A distinguishingfeature of a titanium (IV) titanyl may be the presence of atitanium-oxygen double bond. A titanyl compound may be represented bythe general formula:

wherein R and R′ are each independently selected elements from thePeriodic Table of Elements or one or more functional groups known byindividuals skilled in the art.

Referring to the drawings, FIG. 1 depicts an embodiment of a capable ofreducing the heteroatom content of a heteroatom-containing hydrocarbonfeed. Embodiments of the system 100 may include an vessel 110 which maybe an adsorbent bed, packed with an adsorbent 112. The vessel 110 may beany size, shape or volume. The size, shape and/or volume of the vessel110 may vary depending on the amount of adsorbent 112 being packed intothe vessel 110 and the volume of the hydrocarbon feed expected to beprovided to the vessel 110 for heteroatom removal.

The vessel 110 may be constructed out of any strong, durable orcorrosive resistant material. Such strong, durable or corrosiveresistant materials may include stainless steel or stainless steelalloys, including but not limited to 316 or 316L stainless steel, alloysA-286 (iron nickel-chromium alloy), alloy 20 (nickel, chromium,molybdenum stainless steel), alloy 230 (Nickel, chromium, tungsten,cobalt alloy), alloy 400 (nickel-copper alloy), alloy 600 (nickel,chromium and iron alloy), alloy 600 (nickel, chromium, molybdenum,niobium alloy), alloy B-2/B-3 (nickel molybdenum alloys), alloy c276,nickel 200, tantalum, titanium grades 2, 3, 4, and 7, zirconium 702 andzirconium 705.

As depicted in FIG. 1, the vessel 110 may be filled or packed with asolid adsorption bed of adsorbent 112. Embodiments of the adsorbent 112,although depicted as spherical in the figures, may be prepared anddesigned into any two-dimensional or three dimensional shape. Exemplaryshapes of the adsorbent 112 may be shapes having the highest amount ofsurface area for adsorbing heteroatoms present in a hydrocarbon feed.Examples of shapes may include rods, spheres, pellets, cylinders,multiple lobe shapes including 2-lobe, 3-lobe, 4-lobe, etc., helicaltwisting shapes, cubes, tetrahedrons, hexahedrons, octahedrons,cuboctahedrons, combinations and truncated variations thereof.

Embodiments of the adsorbent 112 may be comprised of any materialcapable of adsorbing one or more different heteroatoms known in the artto be found alongside and mixed with the hydrocarbons and hydrocarbonfeeds disclosed herein, including sulfur and/or nitrogen containingheteroatoms and heterocyclic heteroatoms. In some embodiments, theadsorbent 112 may comprise a metal complex having a central metal atomor ion. Embodiments of the metal complex of the adsorbent may follow thegeneral formula M_(m)O_(m)(OR″)_(n) wherein M is the central atomselected from Ti, Zr, or Hf and R″ at each occurrence may beindividually a functional group having at least one hydroxide. Forexample, the functional groups of R″ may be a substituted alkyl groupcontaining at least one OH group, a substituted cycloalkyl groupcontaining at least one OH group, a substituted cycloalkylalkyl groupcontaining at least one OH group, a substituted heterocyclyl groupcontaining at least one OH group, or a heterocyclylalkyl containing atleast one OH group. The variable m is an integer from 1 to 8 or more;and n is an integer from 1 to 8 or more, as described in US patentpublication US2011/0119988A1, the teachings of which are incorporatedherein by reference, in its entirety.

Consistent with the general formula M_(m)O_(m) (OR″)_(n) someembodiments of the adsorbent 112 may include a metal complex comprisinga titanyl, zirconyl or hafnyl molecule bound to one or more additionalfunctional groups. A chemical formula describing the structure of thetitanyl metal complex may be described as follows:

wherein, R² and R³ are each independently hydrogen or a carboncontaining functional group having at least one OH moiety. For example,in some embodiments of the titanyl the moieties substituted for R² andR³ may include one or more alcohols, diols or other polyol moietiesattached to the central titanium metal atom of the metal complex. Insome embodiments, an alcohol may have the general formula ROH where R isa carbon chain between C₁-C₃₀ or more. A diol may be an alcohol havingtwo OH groups and may be represented by the general formula R(OH)₂. Apolyol may refer to a type of alcohol having two or more OH moietiesbound to the carbon chain R. An example of a general formula of a polyolmay be R(OH)_(x), wherein x>1, such as a vicinal diol. Likewise, azirconyl or hafnyl may follow the same general formula as the titanyldescribed above, however instead of titanium representing the centralmetal atom, zirconium or hafnium may be substituted.

Specific examples of alcohols, diols or other polyol moieties that maybe part of the metal complex of the adsorbent may include glycerol,ethylene glycol, propylene glycol, diethylene glycol, dipropyleneglycol, dithioerythritol, axomadol, azidamfenicol, alfatradiol,bronopol, 1,4-butynediol, capsidiol, chloramphenicol,cyclohexane-1,2-diol, cyclohexanedimethanol, estradiol, ethambutol,methane diol, triethylene glycol, methanol, ethanol, propanol, butanol,pentanol, hexanol, hetpanol, oxanol, polypropylene glycol, 1,2-propyleneglycol, glycerine, trimethylolpropane, pentaerythritol, sorbitol,sucrose other sugars and combinations thereof.

In one or more embodiments, wherein the adsorbent 112 may be comprisedof a titanyl having the metal Ti molecule bound via a double bond tooxygen, forming an oxotitanium(IV) with two constituent polyalcoholfunctional groups (OR², OR³) bound to the titanium atom, the adsorbentmay be described generally by the nomenclaturebis(polyol)oxotitanium(IV). As the embodiment of the polyol present inthe general formula changes for OR² and OR³, the change in the polyol ofthe general formula may be reflected in the name of a particularembodiment. For example, in an embodiment of an adsorbent 112 having atitanyl and glycerol substituted for the polyol, the adsorbent 112 maybe described as bis(glycerolato)oxotitanium (IV). The nomenclature mayuse “glycerolato” instead of “glycerol” because when the glycerol bindsto the titanium atom, one of the hydrogens of the glycerol's OH groupsmay be removed in order to covalently bind to the central titanium atom.Likewise, continuing with the pattern of the nomenclature as described,if instead of using glycerol, ethanol, propanol or butanol were used,the resulting adsorbent 112 may be referred to asbis(ethanolato)oxotitanium (IV), bis(propanolato)oxotitanium (IV) andbis(butanolato)oxotitanium (IV) respectively. Other examples ofadsorbents may include bis(sorbitolato)oxotitanium(iv),bis(erythritolato)oxotitanium (IV) and bis(mannitolato)oxotitanium(IV).

Embodiments of adsorbents 112 may further include a support materialbound to the metal complex. In some embodiments, the support may includeone or more inorganic oxides as the support. The inorganic oxide supportmay include oxides of elements of groups I-A, I-B, II-A, II-B, III-A,III-B, IV-A, IV-B, V-A, V-B, VI-B, VII-B, and VIII-B, of the PeriodicTable of the Elements. For example, inorganic oxides may include, butnot limited to copper oxides, silicon dioxide, aluminum oxide, and/ormixed oxides of copper, silicon and aluminum, Li₂O, Na₂O, K₂O, Rb₂O,Cs₂O, Fr₂O, BeO MgO, CaO, SrO, BaO, ZrO₂, TiO₂, talc and/or combinationsthereof.

The amounts of the adsorbent 112 containing the metal complex and aninorganic oxide support may be adjusted to a mass ratio between themetal complex and inorganic oxide support. In some embodiments, the massratio between the metal complex and the inorganic oxide support of theadsorbent 112 may be within a range of 0.1:99.9 to 99:1. For example insome embodiments, the mass ratio of the metal complex to support may be0.1:99.9, 0.5:99.5, 1:99, 10:90. 25:75, 30:70, 40:60, 50:50, 60:40,70:30. 75:25, 90:10, 99:1, 99.5:0.5, 99.9:0.1 and any ratio in between.

In some embodiments, the adsorbent 112 may be activated to an activatedadsorbent by being treated with a hydroperoxide or peracid. Examples ofsuitable hydroperoxides and peracids may include, but are not limitedto, hydrogen peroxide, tert-butyl hydroperoxide, tert-amylhydroperoxide, ethylbenzene hydroperoxide, cumyl hydroperoxide,tetrahydronaphthalene hydroperoxide, and other organo-hydroperoxidesknow by those skilled in the art, performic acid, peracetic acid, andother per-acids known by those skilled in the art. Embodiments of atitanyl metal complex, once activated into an activated adsorbent mayproduce a peroxytitanate which may follow the general formula:

wherein R¹ is a hydrogen or carbon containing functional group, R² andR³ are each independently hydrogen or a carbon containing functionalgroup having at least one OH moiety. Similar to the R² and R³ describedabove for the titanyl adsorbent 112, the R² and R³ of activatedadsorbent may also be substituted with one or more alcohols or polyolsas described above. Furthermore, in an embodiment wherein the activatedadsorbent is further bound to a support material, at least one of OR² orOR³ may be bound to an inorganic oxide support. Likewise, wherein thestarting metal complex is a zirconyl or hafnyl, the correspondingzirconyl or hafnyl may be activated in the same manner as the titanyland follow a similar general formula, whereby the Ti atom is replacedwith a Zr or Hf atom respectively.

Embodiments of the activated adsorbent's metal complex may be generallydescribed using the general nomenclature(hydroxy)bis(polyol)(hydroperoxo)titanium(IV) or(hydroxy)bis(polyol)(organoperoxo)titanium(IV). The substitution of thepolyol may be dependent on the polyol used to form the activatedadsorbent complex, while the substitution of the hydroperoxo ororganoperoxo group may depend on the type of hydroperoxide or peracidused to activate the adsorbent 112 into an activated adsorbent. Forexample, in some embodiments, the adsorbent may be derived from atitanyl metal complex having glycerol substituted from OR² and OR³ andthus start out as bis(glycerolato)oxotitanium(IV) as described above.Subsequently, the bis(glycerolato)oxotitanium(IV) may be activated bybeing contacted with a peracid or hydroperoxide. For instance,tert-butyl hydroperoxide. The resulting activated adsorbent may bereferred to as (hydroxy)bis(glycerolato)(tert-butylhydroperoxo)titanium(IV) having the chemical structure:

Likewise, if the starting adsorbent 112 was the titanyl metal complexbis(sorbitolato)oxotitanium(IV) and the titanyl was activated with thesame tert-butyl hydroperoxide as described immediately above, theresulting activated adsorbent may be similarly described as a(hydroxy)bis(sorbitolato)(tert-butyl hydroperoxo)titanium(IV).

Similar to substituting the alcohol or polyol group, the nomenclature ofthe activated adsorbent may change by changing the selectedhydroperoxide or peracid as well. Using thebis(sorbitolato)oxotitanium(IV) as the starting material, however thistime instead of using tert-butyl bydroperoxide, a cumyl hydroperoxide isused to activate the adsorbent, the resulting activated adsorbent may bereferred to as (hydroxy)bis(sorbitolato)(cumyl hydroperoxo)titanium(IV).Accordingly, a person skilled in the art should understand from theseexamples the changes in name that would result from the differentcombinations of alcohols/polyols and hydroperoxides/peracids that may beused to construct the adsorbent and activated adsorbent.

Embodiments of the adsorbents and activated adsorbent described abovemay be capable of binding heteroatoms present in a hydrocarbon feed orstream.

One particular and unexpected effect of the disclosed adsorptionmaterial and activated material is the ability of the describedadsorbents to selectively adsorb a particular heteroatom compound, classof heteroatom compounds, or heteroatoms having a particular physicalcharacteristic (such as molecular size). The adsorbent and activatedadsorbent may be selectively tuned or selected for the presencedifferent heteroatom compounds by adjusting the particular alcohol orpolyol functional groups attached to the metal complex. A particularalcohol or polyol functional group may be selected having a higheraffinity for the characteristics of the heteroatom compound beingadsorbed. For example, an alcohol or polyol may be selected with avarying strength of adsorption, strong or weak electrostatic attractionto classes of heteroatom compounds or restrict access of adsorption to aparticular sized heteroatom compound. Using the adsorbents disclosedherein, a person skilled in the art could select the functional groupsof the metal complex in the adsorbent (for OR² and OR³) based on theproperties of the alcohols and polyols and the particular interactionssaid alcohol, polyol or other functional groups may impart on theheteroatoms present in the hydrocarbon feed. In some embodiments, amixture of multiple different adsorbents 112 or activated adsorbents maybe present in vessel 110 in order to modulate the selectively and/orhigh affinity for the heteroatoms and heteroatom classes present in thehydrocarbon feed being treated by system 100.

In some embodiments, the metal complex of the adsorbent may be capableof binding sulfur or nitrogen containing heterocycle compounds mixedwith the hydrocarbon fluid. A heterocycle may refer to cyclic compoundshaving a closed chain or ring of atoms, wherein one of the atoms in thechain or ring is not a carbon atom, but rather a heteroatom such asnitrogen, sulfur, iron, oxygen, vanadium, etc. This adsorbing propertyof the metal complex and activated adsorbent, in particular titanyl,zirconyl and hafnyl metal complexes may arise due to the nature of thealcohol, diol or polyol bonds with the titanium or other metal at thecenter of the metal complex. Examples of removable heterocycle compoundsmay include aziridine, azirine, thiirane, thiirene, diazirine,oxaziridine, azetidine, azete, thietane, thiete, diazetidine,dithietane, dithiete, pyrrolidiine, pyrrole, thiolane, thiophene,imidazolidine, imidazole, pyrazole, pyrazolidine, oxazolidine, oxazole,isooxazolidine, isoxazole, thizolidine, thiazole, isothiazolidine,isothiazole, dithiolane, triazoles, furan, oxadiazole, thiadiazole,dithiazole, tetrazole, piperdine, pyridine, thiane, thiopyran,piperazine, diazones, morpholine, oxazine, dithiane, dithiine, triazone,trithiane, tetrazine, azepane, azepine, thiepane, thiepine,homopiperazine, diazepine, thiazepine, azocane, azocine, andcombinations of heterocyles thereof.

Referring back to FIG. 1, the system 100 used for reducing theheteroatom content of a hydrocarbon feed, may further include an inlet107 receiving a conduit 105. In some embodiments, the conduit 105 may beconnected to a source or reservoir of a hydroperoxide or a peracid whichmay be used for activating the adsorbent 112 located inside vessel 110.In some embodiments, the source of the hydroperoxide or peracid may bepumped through conduit 105 and enter vessel 110 via the first inlet 107.As the hydroperoxide or peracid is pumped into the vessel 110, thehydroperoxide or peracid may flow over the adsorbent 112 packed withinthe vessel 110, reacting with the adsorbent 112 to form an activatedadsorbent described above. As the hydroperoxide or peracid passesthrough the vessel 110, the unused or remaining hydroperoxide or peracidmay exit the vessel 110 via outlet 115.

Embodiments of system 100 may further comprise a conduit 101 which maybe connected to inlet 103 of the vessel 110. In some embodiments, theconduit 101 may be connected to a source or reservoir of hydrocarbonsand more specifically to a heteroatom containing hydrocarbon mixture.Similar to the hydroperoxide and peracid, the hydrocarbon/heteroatommixture (hereinafter hydrocarbon feed) may be pumped through the conduit101 and enter vessel 110 via the inlet 103. As the hydrocarbon feedenters the inlet 103, the hydrocarbon feed may flow over the adsorbent112 or activated adsorbent, making contact with said adsorbent. Whencontact is made between the adsorbent 112 or activated adsorbent and theheteroatoms of the hydrocarbon feed, the heteroatoms present in thehydrocarbon feed may adsorb to the adsorbent 112 or activated adsorbent,removing and separating the heteroatom from the hydrocarbon feed as thehydrocarbon feed continues to flow through vessel 110, until thehydrocarbons exit via outlet 115 as effluent 113. The resulting effluent113 exiting the outlet 115 may have a reduced heteroatom contentcompared to the hydrocarbon feed entering vessel 110 at the inlet 103.

Although the exemplary embodiment depicted in FIG. 1 depicts multipleconduits 101, 105 and multiple inlets 103, 107, an alternativeembodiment may use a single shared conduit (not shown) and inlet totransport and deliver the hydrocarbon feed, hydroperoxide and/or peracidto the vessel 110, however the two feeds 101 and 105 are not fedsimultaneously, but rather consecutively. The two steps may optionallybe repeated as desired.

FIG. 3 provides a flow chart describing an embodiment of a method 300that may be performed using system 100 described above. In step 301 ofmethod 300, the step of providing an adsorbent 112 may be performed bypacking vessel 110 with adsorbent 112 by placing the adsorbent 112inside vessel 110. In alternative embodiments, step 301 may be performedby purchasing or building vessel 110 with the adsorbent 112 pre-packedinside. In step 303, the adsorbent 112 provided in step 301 may becontacted with a hydroperoxide or peracid. The step of contacting theadsorbent 112 may be performed by introducing the hydroperoxide orperacid into vessel 110 via inlet 107 and flowing the hydroperoxide orperacid through the vessel 110 until it reaches outlet 115. Anyremaining hydroperoxide and peracid may be ejected from vessel 110through outlet 115. As the hydroperoxide or peracid flows through thevessel 110, the hydroperoxide or peracid may contact the adsorbent andactivate the adsorbent, forming an activated adsorbent in step 305.

After the activated adsorbent is formed in step 305, a contacting step307 may be performed by introducing a hydrocarbon feed containing amixture of one or more heteroatoms therein, into vessel 110 via thesecond inlet 107. As the hydrocarbon feed is introduced into the vessel110. The hydrocarbon feed may flow through vessel 110, creating contactbetween the activated adsorbent and the hydrocarbon feed having one ormore heteroatoms present in the feed, which may include one or moreheterocycles containing sulfur or nitrogen in some embodiments. As aresult of the contacting step 307, in step 309 the heteroatoms presentin the hydrocarbon feed passed through the vessel 110 may bind to theactivated adsorbent.

The step of contacting the hydrocarbon feed with the adsorbent in step307 may be performed at a sufficient temperature and for an ample amountof time for the heteroatoms present in the hydrocarbon feed to proceedwith binding to the adsorbent in step 309. The temperature of the vessel110 may be about 0° C. to about 100° C., and about 20° C. to about 50°C. in the exemplary embodiments described in the examples below. Theresidence time may vary from as little as about 30 seconds to about 90minutes, while in the exemplary embodiments the residence time may beabout 2 to about 15 minutes. The pressure may be about 0.1 atmospheresto about 10 atmospheres, however in the exemplary embodiments shown inthe examples below, the contacting and binding steps may be performed atapproximately atmospheric pressure.

As the hydrocarbon feed passes through the vessel 110, steps 311 and 315may be performed simultaneously or nearly simultaneously. First, as thehydrocarbon feed passes through the vessel 110, the heteroatoms presentin the hydrocarbon feed may bind to the activated adsorbent in step 309,forming a heteroatom-bound adsorbent in step 311. The heteroatom-boundadsorbent of step 311 may include nitrogen heterocycles and sulfurheterocycles bound to the activated adsorbent in some embodiments. Theheteroatom-bound adsorbent formed in step 311 may remain behind insidethe vessel 110 until removed.

As a result of the heteroatom binding of step 311, the hydrocarbons ofthe hydrocarbon feed may be released from the vessel 110 as effluent113, exiting through outlet 115. As a result of the heteroatoms beingbound to the activated adsorbent in step 311 and the release of thehydrocarbon feed having a reduced heteroatom content from the vessel,step 315 may be performed, wherein the hydrocarbon feed with the reducedheteroatom content is separated and removed from the heteroatom-boundadsorbent, thus ejecting a collectable hydrocarbon feed having a reducedheteroatom content, while the bound heteroatoms remain inside vessel110.

In some embodiments method 300 may result in a reduced heteroatomcontent that is approximately 15% (or less) of the total heteroatomcontent of the hydrocarbon feed entering the vessel 110 via inlet 107.This drastic amount of heteroatom content reduction is demonstratedmultiple times in the examples provided below. As shown in example 1below, a hydrocarbon feed containing 104 ppm of sulfur was reduced to13.5-15 ppm, in example 2 a hydrocarbon feed containing 988 ppm ofsulfur was reduced to 123.2-300 ppm, and in example 3 a hydrocarbon feedcontaining 95 ppm sulfur was reduced to 12.3 ppm-20 ppm. However, theamount of heteroatom reduction may vary depending on the adsorbent 112and activated adsorbent present in the vessel 110, and the temperatureand residence time of the contacting step 307, which may be controlledby the flow rate of the hydrocarbon feed through the vessel 110. As theresidence time increases, an increased amount of heteroatom reductionmay be obtained. The reduced heteroatom content of the hydrocarbon feedmay be less than 99%, less than 90%, less than 80%, less than 75%, lessthan 50%, less than 35%, less than 20%, less than 15%, less than 10%, oreven less than 5% of the heteroatom content of the hydrocarbon enteringinlet 107 of the vessel 110, in some embodiments. Likewise, the totalheteroatom content of the hydrocarbon feed may be reduced by at least a10%, at least a 20%, at least a 30%, at least a 50%, at least a 65%, atleast a 75%, at least an 85%, at least 90% or at least 95%.

In an alternative embodiment of method 300, method 400 may comprise oneor more additional steps. As shown in FIG. 4, steps 301, 303, 305, 307,309, 311, 313 and 315 may remain consistent with steps previouslydiscussed above for method 300. However, additional step 417 may beperformed comprising the addition step of contacting theheteroatom-bound adsorbent formed in step 311 with a solvent. Thesolvent may be any type of solvent capable of extracting the heteroatomsfrom the adsorbent and placing the heteroatom in solution in order toremove the heteroatom from the vessel 110 via outlet 115. Suitablesolvents may include solvents with a Hansen Solubility polarityparameter (δP) preferably in the range of about 0 to 20, and morepreferably in the range of about 1 to 16.

In some embodiments, the solvent may be the same as the hydroperoxide orperacid, or a mixture of a hydroperoxide or peracid previously discussedfor activating the adsorbent 112 with another solvent. In someembodiments, the solvent may be provided to the vessel 110 via conduit105 and enter the vessel 110 through the inlet 107. As the solvent flowsthrough the heteroatom-bound adsorbent, the solvent may extract theheteroatom from the activated adsorbent, flushing the heteroatoms fromthe activated adsorbent. As a result, the heteroatom previously bound tothe activated adsorbent may be removed from the adsorbent in step 419,leaving behind the activated adsorbent as a regenerated activatedadsorbent in step 421. As the solvent flows through the vessel 110,extracting the heteroatom from the activated adsorbent, and placing theheteroatom in the solvent, the heteroatom may be removed from the vessel110 as the solvent exits the vessel 110 via the outlet 115. Accordingly,in some embodiments, the regenerated activated adsorbent formed in step421 may remain inside the vessel 110 and may be subsequently used overand over again as part of method 300 or 400 previously described.

In an alternative embodiment, methods for regenerating aheteroatom-bound adsorbent bed may include diverting the hydrocarbonfeed to a fresh adsorbent bed filled with activated adsorbent, while thefirst bed containing the heteroatom-bound adsorbent is regenerated andthe heteroatoms flushed from the adsorbent bed using a liquid or gassolvent for a time and at a temperature suitable to desorb theheteroatom compounds from the adsorbent bed in accordance with steps417, 419 and 421, placing the regenerated activated adsorbent in acondition suited for reuse. In this way, a continuous stream of thehydrocarbon feed may be subjected to continuous heteroatom removal,without having to stop the hydrocarbon feed in order to performheteroatom removal of the heteroatom-bound adsorbent and regenerationsteps, reducing and eliminating heteroatom removal downtime of thedisclosed method steps.

In an alternative embodiment, method 500, the regenerated activatedadsorbent formed in step 421 of method 400, may be used for furtherrepeatedly reducing the heteroatom content of the hydrocarbon feed or asecond hydrocarbon feed. Similar to methods 300 and 400 described above,the second hydrocarbon feed (or previously treated hydrocarbon feedhaving a reduced heteroatom content) may be pumped through conduit 101into inlet 103. As the second hydrocarbon feed enters the vessel 110,and flows through the vessel 110, the second hydrocarbon feed mayperform step 507, contacting the regenerated activated adsorbent withthe second hydrocarbon feed. Similar to step 307, the contacting step507 may result in the heteroatoms of the second hydrocarbon feed bindingto the regenerated activated adsorbent in step 509.

In some embodiments performing step 509, method 500 may subsequentlyproceed to form a heteroatom-bound adsorbent consistent with step 311discussed above and produce a hydrocarbon feed effluent 113 having areduced heteroatom content that is less than the heteroatom content ofthe second hydrocarbon feed introduced in step 507. The reducedheteroatom containing hydrocarbon feed resulting from the secondhydrocarbon feed may be separated and removed from the vessel 110 in amanner consistent with step 315 described above. Likewise, theheteroatom-bound adsorbent formed as a result of step 509 may beregenerated in manner consistent with steps 417, 419 and 421 describedabove.

In an alternative system 200 depicted in FIG. 2, the system 200 mayinclude a plurality of vessels 110, 210 linked together in series withone another. Linking vessel 110 with vessel 210 via conduit 201 mayprovide an opportunity for further heteroatom removal of the hydrocarbonfeed released as effluent 113, having a reduced heteroatom content fromthe system 100 shown in FIG. 1. In system 200, the hydrocarbon having areduced heteroatom content being released from vessel 110 may be pumpedvia pump 220 to an inlet 203 of vessel 210.

Vessel 210 may be the same type of vessel as previously described abovefor vessel 110. Moreover, similar to the embodiments of vessel 110,vessel 210 may further include an adsorbent 212 packed within the vessel210. The adsorbent 212 may be any type of adsorbent previously describedabove for adsorbent 112, including any and all activated adsorbentspreviously discussed. Embodiments of the adsorbent 112 and adsorbent 212may be identical to one another within system 200, however in someembodiments, the adsorbents 112, 212 may differ between vessels 110 and210. Selection of different adsorbents 112, 212 within vessel 110, 210may be useful for binding different types of heteroatoms. For example, auser of system 200 may target a specific type of heteroatom in the firstvessel 110 and subsequently seek to remove a second type of heteroatomin the second vessel 210. For instance, in some embodiments, theadsorbent 112 selected in vessel 110 may have a higher affinity forsulfur containing heterocycles whereas the adsorbent 212 selected invessel 210 may have a higher affinity for nitrogen containingheterocycles (or vice versa).

Embodiments of the adsorbent 212 may also be activated in a mannersimilar to the adsorbents present in vessel 110. For example, in someembodiments, a hydroperoxide or peracid may be introduced into thesecond vessel 210 via a conduit 205 and inlet 207. Similar to theadsorbent in vessel 210, the hydroperoxide or peracid flowing throughthe vessel 210 may activate the adsorbent in the manner described aboveand any excess hydroperoxide or peracid may be ejected via outlet 215.

The hydrocarbon effluent 113 being pumped through conduit 201 may entervessel 210 and pass through vessel 210, making contact with theactivated adsorbent as the effluent hydrocarbon feed from vessel 110passes through vessel 210. As the effluent hydrocarbon feed passesthrough the vessel 210, the residual heteroatoms that were not bound theactivated adsorbent in vessel 110, may be subsequently bound to theactivated adsorbent of vessel 210, forming a heteroatom-bound adsorbent,similar to the manner previously described for system 100. Thehydrocarbon feed entering via inlet 203 may exit vessel 210 as effluent213. The effluent 213 may subsequently have a reduced heteroatom contentthat is less than both the heteroatom content of effluent 113 and thehydrocarbon feed that entered vessel 110 through inlet 101.

Simultaneously, or near simultaneously as effluent 113 is being pumpedto vessel 210, in some embodiments, the regeneration of theheteroatom-bound adsorbent of vessel 110 may be regenerated inaccordance with the methods 400 and 500 discussed above. However, insystem 200, as the solvent having the dissolved heteroatoms exits outlet115, the solvent and heteroatoms may be purged from system 200 via purgevalve 217 as either waste 219 or sent to another process for recyclingof the solvent which may be returned to system 200 to activate theadsorbent 112, 212 or dissolve heteroatom-bound adsorbents of vessel 110or vessel 210.

FIG. 6 of the present disclosure further describes the method steps foradsorption, removal and regeneration steps of system 200. Using theembodiment 600 as an example, in step 601, each of the vessels 110 and210 may be packed with adsorbent 112, 212 or purchased pre-packed withthe adsorbent of choice. In step 602, a hydroperoxide or peracid may bepumped into vessel 110 via conduit 105, activating an adsorbent bedcontaining the adsorbent 112, 212 in step 605.

In step 606, a hydrocarbon feed may be pumped through conduit 101 intoinlet 103 of the vessel 110. As the hydrocarbon feed flows throughvessel 110, the hydrocarbon feed may contact in step 607, the activatedadsorbent present in vessel 110 as a result of step 605. As a result ofstep 607, in step 613, a hydrocarbon feed with a reduced heteroatomcontent may exit the adsorbent bed of vessel 110 as effluent 113,leaving behind the heteroatoms bound to the activated adsorbent in step611. In step 614 of method 600, pump 220 may pump the reduced heteroatomcontaining hydrocarbon as effluent 113 to the second adsorbent bed 210via conduit 201.

In step 624 of the method 600, the effluent 113 may pass through vessel210 and bind the remaining heteroatoms present in effluent 113 to theactivated adsorbent of vessel 210, resulting in the formation ofheteroatom-bound adsorbent inside vessel 210. In step 626, the effluenthydrocarbon 213 may be ejected from the second vessel 210 having areduced heteroatom content or as a heteroatom-free hydrocarbon. Thehydrocarbon effluent 213 may be sent for further processing orheteroatom removal downstream as needed.

As the effluent 113 is being pumped to the second adsorbent bed ofvessel 210, the heteroatoms bound to the adsorbent bed of vessel 110 maybe removed. Starting in step 616, the solvent may be pumped into vessel110 via conduit 105. The solvent may enter the vessel 110 and in step618, the heteroatoms bound to the adsorbent of vessel 110 may beextracted from the adsorbent and mixed into the solvent passing throughthe vessel 110. In step 620, the solvent containing the heteroatomsremoved from the adsorbent may be ejected from the adsorbent bed ofvessel 210 and purged via purge vale 217 in step 622 as waste or forfurther recycling.

The following working examples are provided for illustrative purposes.The working examples are intended to be non-limiting and are intended tofurther explain and assist in clarifying one or more of the elements ofthe embodiments described above in the current disclosure:

Example 1 Removal of Sulfur from Kerosene to Produce Ultra-Low SulfurDiesel

A packed bed was prepared containing an adsorbent having abis(glycerolato)oxotitanium(IV) coated onto silica (4.1 grams), whichhad been previously contacted with tert-butyl hydroperoxide in toluene.The void volume in the bed was found to be 5.8 mL. A kerosene feed with104 ppm sulfur was flowed through at room temperature and atmosphericpressure, with a residence time of 5 minutes. The first bed volumecontained 13.5 ppm sulfur, and 12.2 bed volumes of kerosene exited thebed with less than 15 ppm sulfur. Pentane was flowed over the bed toremove any residual kerosene (about 5 bed volumes). 3 bed volumes of a10 wt. % solution of tert-butyl hydroperoxide in toluene was flowed overthe adsorbent and collected. Another 3 bed volumes of pentane was flowedover the bed to remove any residual hydroperoxide, then air was blownthrough the bed to thoroughly dry the pentane off. A second pass of 104ppm sulfur-containing kerosene was flowed over the same bed of adsorbentat 20° C. and atmospheric pressure. The first bed volume contained 4.1ppm sulfur, and a total of 19.7 bed volumes exited the column with asulfur content less than 15 ppm.

Example 2 Removal of Sulfur from a Heavy White Oil

An experiment was performed identically to Example 1, except that aheavy white oil feed with 988 ppm sulfur was flowed through a similarlyprepared packed bed of adsorbent. The first bed volume contained 123.2ppm sulfur, and approximately 4 bed volumes of white oil exited the bedwith sulfur below 300 ppm. Pentane was flowed over the bed to remove anyresidual kerosene (about 5 bed volumes). 110 ml of 10 wt. % solution oftert-butyl hydroperoxide in toluene was flowed over the adsorbent andcollected. Another 3 bed volumes of pentane was flowed over the bed toremove any residual hydroperoxide, then air was blown through the bed tothoroughly dry the pentane off. A second pass of 988 ppmsulfur-containing heavy white oil was flowed over the same bed ofadsorbent at 20° C. and atmospheric pressure. The first bed volumecontained 23.8 ppm sulfur, and a total of about 5 bed volumes exited thecolumn with a sulfur content less than 100 ppm.

Example 3 Removal of Sulfur from Dicyclopentadiene (DCPD) to ProduceUltra-Low Sulfur Dicyclopentadiene

DCPD is a reactive feed that would decompose if heated or contacted withhydroperoxides. A packed bed was prepared containing an adsorbentconsisting of bis(glycerolato)oxotitanium(IV) coated onto silica (4.1grams), which had been previously contacted with tert-butylhydroperoxide in toluene. The void volume in the bed was found to be 5.0mL. A DCPD feed with 95 ppm sulfur was flowed through at roomtemperature and atmospheric pressure, with a residence time of 5minutes. The first bed volume had 12.3 ppm sulfur, and 8 bed volumes ofDCPD exited the bed with less than 20 ppm sulfur. Pentane was flowedover the bed to remove any residual DCPD (about 3 bed volumes). 20 bedvolumes of a 10 wt. % solution of tert-butyl hydroperoxide in toluenewas flowed over the adsorbent and collected. Another 6 bed volumes ofpentane was flowed over the bed to remove any residual hydroperoxide,then air was blown through the bed to thoroughly dry the pentane off. Asecond pass of 95 ppm sulfur-containing DCPD was flowed over the samebed of adsorbent at room temperature and atmospheric pressure. The firstbed volume contained 14.1 ppm sulfur, and a total of 9 bed volumesexited the column with a sulfur content less than 20 ppm. An analysis ofthe material after sulfur removal showed that the composition wasunchanged, except for the reduced sulfur content, and that no undesiredchemical reactions had occurred.

While this disclosure has been described in conjunction with thespecific embodiments outlined above, it is evident that manyalternatives, modifications and variations will be apparent to thoseskilled in the art. Accordingly, the preferred embodiments of thepresent disclosure as set forth above are intended to be illustrative,not limiting. Various changes may be made without departing from thespirit and scope of the invention, as required by the following claims.The claims provide the scope of the coverage of the invention and shouldnot be limited to the specific examples provided herein.

What is claimed is:
 1. An adsorbent composition comprising: a metalcomplex including a titanyl, wherein a titanium molecule of the titanylis covalently bound to an alcohol or a polyol; and an inorganic oxidesupport of the metal complex bound to the titanium molecule of thetitanyl.
 2. The adsorbent composition of claim 1, further comprising ahydroperoxide or peracid bound to the titanyl of the metal complex,wherein the hydroperoxide or peracid covalently is bound to an oxygenmolecule double bound to the titanium molecule.
 3. The adsorbentcomposition of claim 1, wherein the alcohol or the polyol are selectedfrom the group consisting of glycerol, ethylene glycol, propyleneglycol, diethylene glycol, dipropylene glycol, dithioerythritol,axomadol, azidamfenicol, alfatradiol, bronopol, 1,4-butynediol,capsidiol, chloramphenicol, cyclohexane-1,2-diol, cyclohexanedimethanol,estradiol, ethambutol, methane diol, triethylene glycol, methanol,ethanol, propanol, butanol, pentanol, hexanol, hetpanol, oxanol,polypropylene glycol, 1,2-propylene glycol, glycerine,trimethylolpropane, pentaerythritol, sorbitol, sucrose and combinationsthereof.
 4. The adsorbent composition of claim 1, wherein the inorganicoxide support is an oxide having a metal from groups I-A, I-B, II-A,II-B, III-A, III-B, IV-A, IV-B, V-B, VI-B, VII-B, and VIII-B of thePeriodic Table of Elements.
 5. The adsorbent composition of claim 4,wherein the inorganic oxide support is selected from the groupconsisting of Li₂O, Na₂O, K₂O, Rb₂O, Cs₂O, Fr₂O, BeO MgO, CaO, SrO, BaO,ZnO, ZrO₂, TiO₂ and talc.
 6. The adsorbent composition of claim 2wherein the hydroperoxide or peracid is selected from the groupconsisting of hydrogen peroxide, tert-butyl hydroperoxide, ethylbenzenehydroperoxide, cumyl hydroperoxide, tetrahydronaphthalene hydroperoxide,performic acid, peracetic acid and combinations thereof.
 7. Theadsorbent composition of claim 1, wherein the metal complex is selectedfrom the group consisting of bis(glycerolato)oxotitanium(IV),bis(sorbitolato)oxotitanium(iv), bis(erythritolato)oxotitanium (IV),bis(mannitolato)oxotitanium(IV) and combinations thereof.
 8. Theadsorbent composition of claim 2, wherein the metal complex is selectedfrom the group consisting of bis(polyol)(hydroperoxo)oxotitanium(IV),wherein the polyol is glycerol, ethylene glycol, propylene glycol,diethylene glycol, dipropylene glycol, dithioerythritol, triethyleneglycol, ethanol, propanol, butanol, sorbitol or a combination thereofand the hydroperoxide is tert-butyl hydroperoxide, ethylbenzenehydroperoxide, cumyl hydroperoxide, tetrahydronaphthalene hydroperoxideor a combination thereof.
 9. The adsorbent composition of claim 8,wherein the metal complex of bis(polyol)(hydroperoxo)oxotitanium(IV) isbis(polyol)(tert-butyl hydroperoxo)oxotitanium(IV).
 10. The adsorbentcomposition of claim 2, wherein the metal complex comprises a generalchemical structure:

wherein R¹ is a hydrogen or a carbon containing functional group, R² andR³ are each independently hydrogen or a carbon containing functionalgroup having at least one OH moiety and at least one of OR² and OR³ isbound to the inorganic oxide support.
 11. The adsorbent composition ofclaim 2, wherein the metal complex has a chemical structure:


12. A method for reducing a heteroatom content of a hydrocarbon feedcomprising the steps of: providing an adsorbent having a metal complexbound to an inorganic oxide support, wherein the metal complex is atitanyl having a titanium molecule covalently bonded to an alcohol orpolyol; contacting the adsorbent with a hydroperoxide or a peracid,forming an activated adsorbent; contacting the activated adsorbent withthe hydrocarbon feed; binding a heteroatom present in the hydrocarbonfeed to the activated adsorbent, forming a heteroatom-bound adsorbent,leaving behind a hydrocarbon feed having a reduced heteroatom content;and separating the hydrocarbon feed having the reduced heteroatomcontent from the heteroatom-bound adsorbent.
 13. The method of claim 12,further comprising the step: contacting the heteroatom bound adsorbentwith a solvent, the solvent removing the heteroatom from theheteroatom-bound adsorbent, forming a regenerated activated adsorbent.14. The method of claim 13, wherein the solvent is a hydroperoxide orperacid.
 15. The method of claim 13, further comprising the step of:separating the heteroatom dissolved in the solvent from the regeneratedactivated adsorbent.
 16. The method of claim 13, further comprising thesteps of: contacting the regenerated activated adsorbent with a secondhydrocarbon feed; and binding a heteroatom of the second hydrocarbonfeed to the regenerated activated adsorbent.
 17. The method of claim 12,wherein the metal complex is selected from the group consisting ofbis(glycerolato)oxotitanium(IV), bis(sorbitolato)oxotitanium(iv),bis(erythritolato)oxotitanium (IV), bis(mannitolato)oxotitanium(IV) andcombinations thereof.
 18. The method of claim 12, wherein hydroperoxideor peracid is selected from the group consisting of hydrogen peroxide,tert-butyl hydroperoxide, ethylbenzene hydroperoxide, cumylhydroperoxide, tetrahydronaphthalene hydroperoxide, performic acid,peracetic acid and combinations thereof.
 19. The method of claim 12,wherein the metal complex of the activated adsorbent isbis(polyol)(tert-butyl hydroperoxo)oxotitanium(IV),bis(polyol)(ethylbenzene hydroperoxo)oxotitanium(IV), bis(polyol)(cumylhydroperoxo)oxotitanium(IV) or bis(polyol)(tetrahydronaphthalenehydroperoxo)oxotitanium(IV).
 20. The method of claim 12, whereinheteroatom content of the hydrocarbon feed is reduced by at least 85%.